Understanding the Scale of the Single Ion Free Energy [electronic resource] : A Critical Test of the Tetra-Phenyl Arsonium and Tetra-Phenyl Borate Assumption.
Ab Initio Md; Rst Principles Md; Electrolyte; Ions; Solvation Free Energies.
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| Format: | Government Document Electronic eBook |
| Language: | English |
| Published: |
Washington, D.C. : Oak Ridge, Tenn. :
United States. Department of Energy. Office of Basic Energy Sciences ; distributed by the Office of Scientific and Technical Information, U.S. Department of Energy,
2018.
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| Subjects: |
MARC
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| 245 | 0 | 0 | |a Understanding the Scale of the Single Ion Free Energy |h [electronic resource] : |b A Critical Test of the Tetra-Phenyl Arsonium and Tetra-Phenyl Borate Assumption. |
| 260 | |a Washington, D.C. : |b United States. Department of Energy. Office of Basic Energy Sciences ; |a Oak Ridge, Tenn. : |b distributed by the Office of Scientific and Technical Information, U.S. Department of Energy, |c 2018. | ||
| 300 | |a Article No. 222819 : |b digital, PDF file. | ||
| 336 | |a text |b txt |2 rdacontent. | ||
| 337 | |a computer |b c |2 rdamedia. | ||
| 338 | |a online resource |b cr |2 rdacarrier. | ||
| 500 | |a Published through SciTech Connect. | ||
| 500 | |a 03/23/2018. | ||
| 500 | |a "pnnl-sa--132440" | ||
| 500 | |a Journal of Chemical Physics 148 22 ISSN 0021-9606 AM. | ||
| 500 | |a Timothy T. Duignan; Marcel D. Baer; Christopher J. Mundy. | ||
| 520 | 3 | |a Free energies, enthalpies and entropies of ions in solution can be experimentally determined for neutral pairs. For individual ions however, determining these properties requires additional assumptions, which can and should be theoretically tested. The tetra-phenyl arsonium and tetra-phenyl borate (TATB) assumption is a commonly used extra-thermodynamic assumption, which allows these values to be split into cationic and anionic contributions. The assumption is that the values for the TATB salt can be divided equally. This is justified by arguing that these large hydrophobic ions will cause a symmetric response in water. Experimental and classical simulation work has raised potential flaws with this assumption, indicating that hydrogen bonding with the phenyl ring may favor the solvation of the TB-anion. In this study, we perform <em>ab initio</em> molecular dynamics (AIMD) simulations of these ions in bulk water demonstrating that there are significant structural differences. We quantify our findings by reproducing the experimentally observed vibrational shift for the TB-anion and confirm that this is associated with hydrogen bonding with the phenyl rings. Finally, we demonstrate that this results in a substantial energetic preference of the water to solvate the anion. In conclusion, our results suggest that the validity of the TATB assumption, which is still widely used today, should be reconsidered experimentally in order to properly reference single ion solvation free energy, enthalpy and entropy. | |
| 520 | 0 | |a Ab Initio Md; Rst Principles Md; Electrolyte; Ions; Solvation Free Energies. | |
| 536 | |b AC05-76RL01830. | ||
| 536 | |b AC02-05CH11231. | ||
| 650 | 7 | |a Inorganic, Organic, Physical, And Analytical Chemistry. |2 edbsc. | |
| 710 | 2 | |a Pacific Northwest National Laboratory (U.S.). |4 res. | |
| 710 | 1 | |a United States. |b Department of Energy. |b Office of Basic Energy Sciences. |4 spn. | |
| 710 | 1 | |a United States. |b Department of Energy. |b Office of Scientific and Technical Information. |4 dst. | |
| 856 | 4 | 0 | |u http://www.osti.gov/scitech/biblio/1492309 |z Online Access (via OSTI) |
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